Lactone-derived compounds of certain oxyalkylated resins and method of making same



July 12, 1960 M. D'E GROOTE ETAL LACTONE-DERIVED COMPOUNDS OF CERTAINOXYALKYLATED RESINS AND METHOD OF MAKING SAME Original Filed 001;. 5,1953 HENOL-ALDEHYDE P RESIN l00% United States Paten L'ACTONE DERIVED.CGNIPOUNDS; 'OF OXYALKYLATEDxRESINS AND METHOD QF; MAKING SAME a MelvinDe Groote, St. Louis, and'Kwan-Ting Shen, Brentwood, Mo., assignors toPetrolite Corporation; Wilmingfon, Deli, a co poration of- Delaware 7ori inal application Oct. '5, lasalser. No. 334,307. Di-

Vidal and 626,616 I 9 Claims. (Cl. 260-53) This application is adivision of our copending appli cation Serial No. 384,307, filed October5, 1953, Patent No. 2,888,403. j Y I The present invention is concernedwith a process for chemically modifying certain polyols, as hereinafterspeci fled, with beta propiolactone,-'or its equivalent, under sub-'stantially anhydrous conditions in'the absence of a basiccatalyst andpreferably in the presence of an acid catalyst, to yield' fusible(non-therniosetting) derivatives. The polyols employed are oxyalkylated'hydrophile syntheticderivatives of certain phenol-aldehyde resins. Theendproducts obtained by treatment of" propiolactone, or'the like, arevaluable for the resolution of petroleum emul' sions of the water-in-oiltype and also for application:

in various industrial arts as hereinafter specified. V

The preparation of hydrophilesynthetic products which are in essencepolyols by the oxyalkyl'ation of phenol aldehyde resins is well knownand "has been described in considerable detail in a large numberofUnited States I instance, United States Patents Nos:

patents; for 2,499,365, 2,499,366, 2,499,367, 2,499,368 and 2,499,370,"all. dated March 7, 1950, and all to De Groote and Keiser. The preferredtypes and those particularly'suit- 2,945,005 Patented July 12, 1960Stated another way, the lactones which are suitable are.

.. formula this application Dec. 6, 1956, Sel'. No. i

the beta-lactones of monocarboxylic acids having'at least oneunsubstituted hydrogen atom on the alpha-carbon atom and containing onlyunreactive hydrocarbon substituents.. structurally, these beta lactonespossess the wherein R is a hydrogen or an. unreactive hydrocarbonradical such as alkyl, aryl, aralkyl, or a cycloalkyl radical. Includedin this class of compounds are the beta-lactones of saturated aliphaticmonocarboxylic acids containing at least one hydrogen atom on the alphacarbon atom such as beta-propiolactone, beta-butyrolactone,alphamethyl-beta-propiolactone,' beta valerolactone, alphamethylbutyrolactone, alpha-ethyl-beta-propiolactone,. beta-isovalerolactone,beta-n-caprolactone, alpha-methyl beta-valero-lactone,beta-methyl-beta-ethyl-beta-propio- 1 beta-lactones of aryl-substitutedcarboxylic acids such as able for the present purpose are thosedeseribedin the last mentioned patent with the proviso that the substituent radical may have as many as 18 carbon atoms; Reference is made alsoto US. Patent No; 2,557,081; dated June, 1951, to De Groote and Keiser.

Briefly stated, the manufacturing method herein-employed is to react anoxyalkylated phenol resin ofthe kind described in the variousabovementioned patents with beta-propiolactone or its equivalent inaratio so there are employed preferably at least two moles of thelactone for each oxyalkylated resin molecule.

In our co-pending applications, Serial Nos. 343,804,v now abandoned,filed March 20, 1953, and 349,972, filed- April 20, 1953, Patent No.2,792,353, we have described more complicated oxyalkylation derivativesin which oxyalkylated resins were united by means ofa poly-' epoxide,particularly a diglycidyl ether. Such Ipolyepoxide derivatives also maybe treated with a suitable beta-lactone in the manner herein described.The resultant products are suitable for the same purposeand particularlyfor the resolution of petroleum emulsions of the water-in-oil type.

As far as we are aware the only suitable beta-lactone. commerciallyavailable is beta-propiolaetone. Other similar latcones and particularlythose having less than 6 carbon atoms, such as beta butyrolactone and'betamethyl-beta-butyrolactone, can be prepared by any. well knownprocedure such as described, for example, in U.S. Patent No. 2,469,110,dated May 3, 1949, to .Hagemeyer, Jr-

A number of other beta-lactones could be employed and particularly thosehaving less than 6 carbon 'atomst beta-phenyhbeta-propiolaotone,alpha-phenyl-beta-propio-. lactone, and other beta-lactones ofsubstituted carboxylic. acids such asbeta-cyclohexyl-beta-propiolactone, beta benzyl-beta-propiolactone,alpha-cycloheXyl-beta-propim lactone and the like. The preferredcompounds are the beta-lactones containing less than 6 carbon atoms,particularly the low molecular weight aliphatic beta-lactones since thedifiiculty of carrying out the reaction is increased whenemployinglactones of higher molecular weight. Reference is made to thefact that no attempt has been, made to point out the exact nature, atleast quantitatively, of the modification which takes place when apolyol is) reacted with beta-propiolactone or the like. The pro-L ceduresimply hasbeen referred to as chemically modi fyingthe polyol.

Returning now to a comparable reaction, except that. obviously it ismore simple, is the one involving a monohydricalcohol such as methanoland .propiolactone; The action of an alcohol varies with the pH. In

alkaline solution a glycollic ester, and in acid solution aglycollicether is produced:

In all these reactions a certain amount of polymeric material, e.g.

excess the yield of the beta-alkoxymonocarboxylic acid obtained-may beand oftenconsiderably less. See' US. Patent No. 2,352,641, dated July 4,1944, to Kung.

In the case of a monohydric reactant employing acid as acatalyst threetypes of reactions take place, depending on 'whether the 4-membered ringsplits between the oxy-' g'en -atom andthe carbonyl carbon atoms, ortheoxygen atom and the adjacent methylene carbon atom. This has beenillustrated sometime, thus:

+Ronf noonionlooon i A beta'alkoxypropionic acids nooraomcoon cniolii'co(See B. F. Goodrich Chemical Company Service Bulle- 47--SD5 November 1,1947.)

Dehydration, of course, "depends on the temperature employed and otherconditions. See .also 'Journal'of American Chemical Society, vol. 70,page 1004 (1948). '.The third reaction is simply one of polymerizationas has been pointed out in U.S. Patent No. 2,526,554, dated October 17,1950, to Gresham and Jansen. For instance, the patent states as follows:7

; Polyester acids produced by the reaction of an excess ofbeta-propiolactone with an alkanol (R OH) in the presence of an acidcatalyst. Such polyester acids pose sess the formula wherein R is analkyl radical such. as methyl, ethyl, propyl, butyl, etc. ,7 V f .When amore complicated reactant is employed, as in the present instance,i.e.,' a certainspecified variety of apolyhydric alcoholis used, furthercomplications may appear. It is necessary to only point out that a freecar: boxyl radical resulting from a reaction'of the kind previouslydescribed,. could combine with an .unconverted alcoholic hydroxyl toform a polyester. Indeed, the ,best statement in regard to the situationinvolving propriolactone or its equivalent and polyhydroxy compounds isstated in U.S. Patent No. 2,455,731, dated December, 7,

1948, to Caldwell, in the following language:

It is known that beta-lactones react with monohydric alcohols to producebeta-alkoxy carboxylic acids :which may be converted to analpha-beta-unsaturated carboxylic acid ester, as shown by Kung in U.S.Patent 2,352,641, dated July 4, 1944. It is also known that bet'alactones may be readily polymerized to thick, viscous, semi-solid'polymers which maysubsequently be hydrolyzed and- "a,946,oos,

7 Actually, the situation is more involved than suggested by what hasbeen said previously, by reference to the above patents. See JournalAmerican Chemical Society, volume 70, page 1004 (1948), and JournalAmerican Chemical Society, volume 73, page 4273, (1951).

As far as we have been able to determine we have found no conditionunder which one could, for example,

introduce: a single ca'rboxyl radical for each reactive hy' droxyl"radical present without simultaneously producing one or more otherderivatives in an amount equivalent to thecarboxy derivative. .In otherwords, starting with a ratio-of one mole of beta propiolactone, forexample,

' for each reactive hydroxyl we have found that all likelihoodatleastfive cogeneric types may beformed; 1) a monocarboxylatedderivative; (2)an ester formed by reaction between the monocarboxylated derivative anda hydroxyl group; (3) a hydroxy propionic acid ester;

1 (4) an acid group of the 'type where 2 carboxyls havepoint-doeslnotreveal the simple carboxylic acid alone butfmayr'eveal the:type noted above where-two beta lactone molecules enter at a singlehydroxyl position. Likewise,'when an increased ratio ofbeta-lactone isemployed the type. of acid depicted above may become more complicated.In other words, several moles of beta propiolactone may enter at asingle hydroxyl position and yield anacid radical having a singlecarboxyl group but being of distinctly higher molecular weight. Any ofsuch acid radicals may react with any free hydroxyl. 111-.

1 deed, almost invariably and inevitably in-a cogeneric mix-.

. ethanol radicals,""s-uch polyol could be converted into athermosetting resin of the kind specified in U.S. Patent No. 2,455,731;However, 'we use resins which have been. oxyalkylated to the extent thatthe resultantproduct is permanentlyr fusible and not thermosetting inthe usual sense. Stated another way, the resultant of reaction with vdehydrated to produce alpha-beta-unsaturated carboxylicT I acids, asshown by Kung in U.S. Patent 2,361,036, dated October 24, 1944. I havenow found that beta-propionolactone may be reacted with polyhydricalcohols having 2 to 6 free hydroxyl groups to produce valuable polytriers which may be readily adapted to forming films, inoorporatedv withcellulose esters, cellulose" ethers, vinyl polymers, and the like. Otherbeta-lactones, similar in structure to beta-propionolactone, are notsuitable for preparing the resinous polymers of my invention. It wastherefore most unexpected to find that beta-propionm,

lactone alone gave valuable polymers when reacted with a polyhydricalcohol. Although the mechanism of the condensation has not been fullyinvestigated, it appears thatbeta-propionolactone undergoes somepeculiar formof rearrangement or molecular orientation which is notashown by the higher members of. thebeta-laQtQ lQ ss t esgf; 1? hydarpins: wh a e first eased w h, PPl da the selected beta-lactone yieldsproducts which are or-- ganic solvent-soluble. In other words, theyaresoluble in solvents such as hydrocarbons, particularly aromatichydrocarbons, including xylene, etc. They are generally A soluble inalcohols, ethers, glycols, etherglycols, and the like. These derivativescan be dissolved in a mixed solvent consisting of a mixture of anoxygenated solvent and 'a'nonoxygenated solvent. They can'be prepared atthe temperature of reaction herein described without yielding insolubleresins. Reference to the products be ing obtained at temperatures belowthe'point of pyrolysis, of course, doesnot exclude dehydration as one ofthe usualreactions in light of what has been said previously.Oxyalkylated resins canfbe' treated with polyepo-xides particularlydiglycidyl ethers as described in our copending applications, SerialNos. 349,972, filed April 20, 1953, and 343,804, filed March- 20, 1953.Such oxyalkylated derivativescan be reacted with laotones as hereindescribed in the same manner as compounds free from polyepoxide groups.Thisalso applies to .phenol-alde-' and particularly adiglycidylretlrerrandthenrsiibiecteilito roughly represent two parts ofthe -initial resin and' ninety-eight per cent of the alkylene oxide.

Reference is again made to US. -Batent No. 2,499,368, -.dated March 7,1950, .to De-Groote and :Keiser.- Attention directed to that part of thetext whichappears in columns 28 and 29, lines .12 through '75, and lines51 through 21, respectively. Reference is made tothis test 'withmhe sameforce and elfect. as if it were hereinin- -;cluded. This, in-essence,means --that-the preferred prodruct for resolution .of-petroleumemulsions o'fathe waterinr oil type is characterized -bythe fact that a50-50'solution inxylene or its equivalent, when mixed with one to threevolumes vof water andshaken willproduce :an emulsion.

:For purpose of convenience, whatlis said hereinafter be divided intolive parts:

Part 1 is concerned with suitable phenol-aldehyde "resins'to beemployedfor teactiomwith-monoepoxides;

.Part 2 is concerned with .theoxyalkylationof t'hepreviously describedphenol-aldehyde resins;

Part 3 is concerned with the reactions between the -oxyalkylated resinspreviously described and a suitable lactone such as beta-propriolactone;

"Part -4 is concerned with the 'resolutiono'f petroleum emulsions of thewater-in-oil type -by means of the previously-described chemicalcompounds or reaction pro'ducts: and

Part 5 is concerned with uses #for "the products herein describe'd,either as such or after modification, includ- .ing uses in applicationsother thanthose involving resolution of petroleum emulsions ofthewater-in-oil-type.

PART 1 This :part isco'ncerned with lt'heprepara'tion of phenolaldehyderesins of the -kind'described-in det-ail-inULS.

Patent No. 2,499,370, dated lMarch1,l9.50,ito5De 'Groote :and Keiser,with'the following qualifications: said afore- .-mentioned ';patent 'isIlim'ited to resins obtained from di- Jfunction-al phenols having -4 tol2 carbon-atoms in the substituent hydrocarbon radical. For the ,presentpurpose the substituent may "have as many-as 18 carbon :atoms, as in thecase of resins .preparedfrom tetradecyle "phenol, substantially paratetradecylphenol, commercially available. Similarly, resins :can beprepared .from hexadecylphenol or octadecylphenol. Thisfeaturewill bereferred' to subsequently.

are

hon atom also being very'satisfactory. The increased cost of the C and Ccarbon "atom phenol renders these raw materials of less importance, atleast at the present time.

.Patent 2,499,370 describes in detail methods of pro paring resinsuseful as intermediates for preparing the products of the presentapplication, and. reference is made to that patentfor such detailedidescriptionyand to Examples 1a through 103a of that patent forexamplesof suitable resins.

As previously noted, the'hydrocarbon "substituent in the phenol may'have as "many .as #18 :carbon fiatoms, as illustrated bytetradecylphenol,1;hexadecylphenol and octa- -decy1phenol, reference "ineach instance being to therd-iphenol, .such-cas 'Ithekortho- .or-mra{substituted phenol or a mixture of the same; lrsuchyresin's aredescribed also in issued patents, for instance, US. Patent No.2,499,365, dated March'l, 1950, to De Groote and Keiser, such *asExample71a. It is sometimes desirable to present the resins herein employedin.an over-simplified form which has appeared firom time to time in atheliterature, and particularlyin the patent literature, for instance, ithas been stated that the composition is approximated in an idealizedform'by the formula V in the above formula n representsa small'wholeznumber varying from 1 to 6, 7 or 8, or more, up to probably 10 or12 units, particularly when the resin is subjected'to Jheatingunder avacuum'as described in theliterature. .A limited sub-genus in theinstance of low molecular weight polymers where thetotal number ofphenolnuclei varies from 3 to 6; i.e., n varies- 10ml to 4; R represents.an aliphatic hydrocarbon substituenL-generally an alkyl radical havingfrom 4 to 14 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecylradical. Where the divalent 'bridge radical is shown-as being derivedfrom formaldehyde, it may, of course, be derived fromany-oth'er reactivealdehyde having -8 carbon atoms orless. In the above formula thealdehyde employed in the resin manufacture is formaldehyde. Actually,someother aldehyde-such as acetaldehyde, ,propinoaldehyde,orbutyraldehyde may be used. The resin unit can be exemrplified thus:

in which R'" is the divalent radical obtained from the particularaldehyde employed to form the resin.

As previously stated, the preparation of resins, the :kind hereinemployed as reactants, is well known. See US. Patent No. 2,499,368,dated March 7, 195,0,toDe Groote and Keiser. Resins can be made using anacid catalyst or basic catalyst or a catalyst showing neither acid norbasic properties in the ordinary sense'or .without any catalyst at all.It is preferable :that the resins employed be substantially neutral. Inother words, if ,prepared 'by'using a strong acid-as a catalyst, suchstrong acid should be neutralized. Similarly, if a strong-base is usedas a catalyst it is preferable that the "base be neutralized although wehave found that sometimes the reaction described proceeded morerapidly'in the presence of a small amount of a free base. The amount maybe as small as a'200th of a percent and as'much as .a few th of apercent. Sometimes moderate increase in caustic soda and caustic potashmaybe used. .However, the most desirable procedure in practically everycase is to. have the resin neutral. c

In preparing resins 'one does-notget a single polymet, i.e., onehavingjust 3 units, or just 4 units, or just 5 units, or just 6 units,etc. .It .is usually a :mixture;-for instance, one approximating 4phenolic nuclei willhave some trimer and pentamer present. Thus,themoleeular weight may be such that it corresponds to .a-fractionalvalue for n as, for example, 3.5; 4.5; or 5.2.

"In the actual manufacture of the resins we found no ,reason for usingother than those which are lowest .in @rice and most readily availablecommercially. For -pun e'm'e'nce these sixteen tables TABLE n with 11116first table. For conv axe summarized in the fqllowin'g table:

hracteriz'gd ii:

ins ar c 'table res TABLE I enienc su1 g table:

15086 of Com the follqwin F11 It will be noted that the various-resmsreferred-to in the aforementioned US. Patent 2,499,370. aresubstantially the same type of materials as referred to in Table I. .Forinstance; resin 3a of the table is substantially the same as. 2a of thepatent; resin 20a of the-table is substantially the same as 34a of thepatent; and resin 38a of the table is the sameas 3a of the'patent. Inreaction with .polyepoxide,. and particularly diepoxides, a large numberof the previously described oxyalkylated resins have been employed. Forconvenience, the following list is selected indicating the previouslydescribed compounds and their. molecular weights. Such resins are,generally employed as a 50% solution and the polyepoxide employed is a50% solution, usually both reactants being dissolved in xyleneandsufficient sodium methylate added to act as a catalyst, for instance, 1to 2%.

TA B I IE V 7' I Example Number: Molecular weight 1b 1202 2b 2169 3b3339 -4b 46 09 5b 5749 6b Y 1509 7b 2466 8b 3657 3c 4019 40 6139 50 V7079 1d V 7 V 1697 2d 1918 3d 3189 4d V 23,959 511 a 1 f 239 6d 24,9097d 23,959 8d 9d 1697 PART 3 As stated previously, the final reactioninvolves the group presentin the oxyalkylated molecule.

As is well known, beta-propiolactone reacts readily, in

fact, comparable to the more reactive acid anhydrides. Generallyspeaking, we have conducted the reaction in the presence of an inertsolvent such as benzene, toluene, xylene, or a mixture and at atemperature from the boiling point of water to slightly above thattemperature. Generally speaking, the range of 100 C. to 130 C. isperfectly satisfactory and in any event we have limited the temperatureto 175 or less.

A catalyst is employed, preferably an acid catalyst present in theamount of about .2% to not over 1%. The catalyst can be any suitableinorganic acid such as sulfuric acid, hydrochloric acid, phosphoricacid, or may be an organic acid, suchas an aromatic sulfonic acid,including para-toluble sulfonic acid. It is sometimes convenient to usea mixtureof xylene, and benzene so the mixture doubles'at 120 to 135 C.and permits the reaction mass to'reflux at this temperature in presence,of

.5 catalyst for approximately 2 to 4 hours. At the tralized if desiredand the product can be filtered.

IThe products can bebleached by the use of filtering clays, chars, onthe like-sd as to obtain products having eithera straw color or arealmost water-white. Some of the products have a yellowish amber orreddish shade but this is of no significance for the uses for which theproducts'are usually employed."

The reaction should be conducted under anhydrous or substantiallyanhydrous conditions. Our preference is to dissolve the oxyalkylatedresin, preferably as a neutral product, in a suitable amount of xyleneand benzene and then reflux in presence of the acid catalyst until nowater shows in thephase separating trap. We then prefer to cool theproduct back to 60 C. with continued stirring and add thebeta-pr'opiolactone dropwise and continue 15 stirring and then raise thetemperature up to the reflux point. It is quite pos'siblethat refluxingat the temperature indicated, 130 C., or modestly higher, completes thereaction within one-half to one hour but to be on the safe side we haveinvariably employed a reflux period of 2 to 4 hours. A somewhat highertemperature can be employed, and as the temperature increases it appearsthere is a tendency for the free acid value to drop off. .As pointed outpreviously theproduct of reaction has a saponification value and also anacid value, The saponification value may be due'in part to a polymerizedhydroxy acid radical and also may be due in part to an ester radicalinvolving either an nnpolymerized acid radical or a polymerized acidradical, and a hydroxyl group. There is no objection to using a highertemperature or longer period of time provided only the final productsstill remain soluble in xylene or an equivalent organic solvent.

Using the reactants herein described in the proportions described andunder the conditions described the products of reaction are invariablyorganic solvent-soluble. Even if freed of solvent and heated at asomewhat higher temperature the products are apt to remain fusible orthermoplastic up to their decomposition point, or gelation point.

Example Is In a suitable reaction vessel 122.8 grams of oxyalkylatedresin, previously identified as Example 4c, were mixed with 126 grams ofxylene and one gram of sulfuric acid. The mixture was heated slowly toapproximately 70 C. and then 2.9 grams of beta-propiolactone addedslowly. The temperature was then raised to appro'ximately 125 C. andheld at this point for 2 hours. At the end of this time tests showed thereaction was complete. There was no unreacted beta-propiolactone.

Table VI following gives a large number of examples in tabular formincluding all pertinent data.

The finished product had substantially the same appear- 7 ance as theinitial oxyalkylated resin except that it was somewhat more reddish incolor and a bit more viscous in absence of solvent. In other instancesthere was a definite increase in viscosity, especially when higherratios of lactone were employed.

PART 4 As to the use of conventional demulsifying agents reference ismade to US. Patent No. 2,626,929, dated January 7, 1953, to De Groote,and particularly to Part 3. Everything that appears therein applies withequal force and effect to the instant process noting only thatwherereference is made to Example 13b in said text beginning in column 15 andending in column 18, reference should 'be to Example 4e, hereindescribed.

PART 5 The products, compounds, or the like herein described can beemployed for various purposes and particularly for the resolution ofpetroleum emulsions of the waterm-oil;type as described in detail inPart 4 immediately 1 p eceding.

TAB-LEVI Oxy- CatazSolvent Max. Time alkyl- Amt, Amt, Molar lyst, (Xy-Reaction of Re- Ex. N0. ated gins. Lactone gms. Ratio Oonc. lane),Temp., action Resrn H2804" gms. 0. (hrs.)

1 '4 122.8 -.B'eta-proplo-lactone- 2.9 1:2 1 126 125 2 2! 4!- 122.8 14.41:10 1 137 115 3 28.8 1:20 1 152 110 3 2.9 1:2 1 145 121 2 14.4 1:10 1156 110 3 28.8 1:20 1 170 115 3 1. 5 1:2 2 251 118 2 t 7.2 1:10 2 256115 2 14.4 1:20 2 264 110 3 1.5 1:2 2 241 120 2 7.2 1:10 2 247 116 214.4 1:20 2 250 118 3 10.0 1:5 1 133 125 3 20.0 1:10 1 143 122 4 10.01:5 1 152 122 3 20.0 1:10 1 162 125 4 6.0 1:5 2 254 130 2 10.0 1:10 2259 128 3 5.0 1:5 2 245 123 2 10. 0 1:10 2 250 125 3 Such products canbe reacted with alkylene imines, such as ethylene imine or propyleneimine, to produce cation-active materials. Instead of an imine, one mayemploy what is somewhat equivalent material, to wit, a.dialkylaminoepoxypropane of the structure wherein R, and R" are'alkylgroups.

, It is notnecessaryto point out that after reaction with areactantofithe described whlch introducesa basic nitrogenatom that-theresultant productcan be employed for the resolution of emulsions of thewater-in-oil type as; described? in; Part: 4; preceding; and also forother purposes described hereinafter. I Referringnow tothe use of theproducts obtained by reaction with a beta lactoneand certain specifiedoxyalkylated products obtained in the manner described in Part 3,preceding itis to benoted that in addition to their use in theresolution of petroleum emulsions they may be used as emulsifying agentsfor oils, fats, and Waxes, as ingredients in insecticide compositions,or as detergents andwetting agents in the laundering, scouring, drying,tanning and mordanting industries. They may also be used for preparingboring or metal-cutting oils and cattle dips, as metal picklinginhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but theycan serve as initial materials for more complicated reactions of thekind ordinarily requiring a hydroxyl radical. This includesesterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives tolubricating oils, both those derived from petroleum and syntheticlubricating oils. Also, they can be used as additives to hydraulic brakefluids of the aqueous and non-aqueous types. They may be used inconnection with other processes where they are injected into an oil orgas well for purpose of removing a mud sheath, increasing the ultimateflow of fluid from the surrounding strata, and particularly in secondaryrecovery operations using aqueous flood waters. These derivatives alsoare suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initialresin, the particular monoepoxide selected, and the ratio of monoepoxideto resin, together with the particular polyepoxide employed, result in avariety of materials which are useful as wetting agents or surfacetension reducing agents; as detergents; emulsifiers or dispersingagents; as additives for lubricants, both of the natural petroleum typeand the synthetic type, as additives in the flotation of ores and attimes as aids in chemical reactions insofar that demulsification isproduced between the insoluble reactants. Furthermore, such products canbe used for a variety of other purposes, including use as corrosiveinhibitors, defoamers, asphalt additives and at times even in theresolution of oil-inwater emulsions. They serve at times as mutualsolvents promoting a homogeneous system from two otherwise insolublephases.

Attention is directed tothe fact that the present invention is concernedonly with beta-lactones as described. In a nurnber of instances thereare available, or can be prepared readily, certaingamma-lactones whichundergo somewhat similar reactions and give products having'comparableproperties. We have prepared a number of'such derivatives and find themuseful for the same purposes for which the beta-lactone derivatives areused. How-'- ever, such gamma-lactone derived products are not part ofthe present invention.

Havingthus described our invention what we claim as new and desiretosecure by Letters Patent, is:

l. The chemical manufacturing process which includes reacting in which Ris a hydrocarbon radical having at least 4 and not more than 18 carbonatoms and substituted in the 2,4,6 position; said oxyalkylated resinsbeing characterized by the introduction into the resin molecule of aplurality of divalent radiaetaooa' cals having the formula (R O) inwhich R is a member selected from the class consisting of alkylene oxidebe introduced nucleus;

with

(BB) a beta-lactone of the formula R R R H- i o oo=o I wherein R is aradical selected from the group consisting of hydrogen and unreactivelower alkyl, phenyl, benzyl and cyclohexyl radicals; said reaction beingcon ducted in a substantially anhydrous state in the presence of an acidcatalyst and at a temperature at least about 100 C., and below the pointof pyrolysis"; the products of reaction being organic solvent-soluble;

the molar ratio of reactants being at least i rnoles of A 1 I3. Thechemical manufacturing process of 1 wherein the beta-lactone ispropiolactone. 4. The chemical, manufacturing process of aaja 1groupprwent in the oxyalkylated phenol-aldehyde wherein the beta-lactoneis propiolactone and the reac n xc ss of synthetic products beingoxyal-kylated-resins formed by V turing process defined in claim' 1.

- reactionof (A) both ethylene oxide and propylene oxide; and (B) .anoxyalkylation susceptible, fusible; organic solvent-soluble,water-insoluble phenol-aldehyde resin; said resin being derived byreaction between *adifunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidvphenol being of the fromulain whichRis ahydroc-arbon radical having atleast 4 and not more than '14 carbonatoms and substituted'iaitheiz; jp ssai io sy c t resins being characterizedby the introduction into theresin'niolecule of a'plurality of divalent C H4O and c H o-radicals, thecomposition ofv said hydrophil'slynth'etic products, basedpn astatistical average and assuming-completeness of reaction, andcalculatedback to the jthree oxyallrylation-step reactants, i.e., resin,ethylene oxide and ro lene; oxidefj on" fa percentage; weight basisfalling approximately within the area defined by the trapezoid, '1, 2, 3and 4 of the chart in the accompanying drawing;

Witli":" T (BB) beta-propiolactone; said reaction being conducted in asubstantially anhydrous state in the presence of an acid catalyst and ata temperature of about to C., the products of reaction being organicsolventsoluble, the molar ratio of reactants being at least 2 moles ofthe lactone for each mole of oxyalkylated resin and not inexcess of 6moles of the lactone for each hydroxyl group present in the oxyalkylatedphenol-a1dehyde resin.

6. The chemical manufacturing process of claim 5 wherein the threeoxyalkylation step reactants, i.e., resin, ethylene oxide and propyleneoxide on a percentage basis fall within the area defined by theparallelogram 5, 6, 3 and 7 on the chart in the accompanying drawing.

=7. The product resulting from the-chemical manufac- -8. The productresulting from the chemical manufactu ng process defined in claim 5. I

7 No references cited.

1. THE CHEMICAL MANUFACTURING PROCESS WHICH INCLUDES REACTING (AA)HYDROPHILE SYNTHETIC PRODUCTS, SAID HYDROPHILE SYNTHETIC PRODUCTS BEINGOXYALKYLATED RESINS FORMED BY REACTION OF (A) AN ALPHA-BETA ALKYLENEOXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASSCONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE GLYCIDEAND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE,ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN, SAIDRESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCITIONAL MONOHYDRICPHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVETOWARD SAID PHENOL, SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCEOF TRIFUNCTIONAL PHENOLS, SAID PHENOL BEING OF THE FORMULA